CN109862921A

CN109862921A - Novel amino diphosphonate antiwear additive

Info

Publication number: CN109862921A
Application number: CN201780065496.2A
Authority: CN
Inventors: 约翰·马歇尔·贝克; 纪尧姆·卡朋特
Original assignee: Afton Chemical Corp
Current assignee: Afton Chemical Corp
Priority date: 2016-09-19
Filing date: 2017-09-18
Publication date: 2019-06-07
Anticipated expiration: 2037-09-18
Also published as: KR102619225B1; US10072032B2; US10414784B2; CN109862921B; KR20190058507A; AU2017329026B9; US20180099985A1; US20180370998A1; RU2019110146A3; EP3515516B1; BR112019005181B1; JP2019529404A; WO2018053407A1; AU2017329026B2; RU2019110146A; EP3515516A4; JP7065833B2; MX2019002850A; CA3037345A1; BR112019005181A2

Abstract

The present invention relates to the lubricating additive compositions and lubricant compositions that are suitable for the novel amino bisphosphonate of antiwear additive and/or friction modifiers additive component, respectively contain this kind of compound, and the method for making and using it.

Description

Novel amino diphosphonate antiwear additive

Cross reference to related applications

This application claims September in 2016 19 days the U.S. Provisional Patent Application submitted No. 62/396,465 and 2017 9 U.S. Provisional Patent Application the 15/706th, 498 equity that the moon is submitted on the 15th, the full content of the application is thus with reference Mode be incorporated herein.

Technical field

The present invention relates to the novel amino diphosphonate chemical combination for being suitable for antiwear additive and/or friction modifiers additive component Object, the lubricating additive composition and lubricant compositions for respectively containing this kind of compound, and the method for making and using it.

Background technique

Industry and automobile gear are often subject to cause gear surface and/or the pressure of the abrasion on roller bearings element and bear It carries.In some cases, the stress being applied on gear facilitates microdot erosion, this is a kind of gear fatigue form and common tooth Take turns fault mode.

In general, the gear train fluid that needs specially to deploy meets performance requirement.For reduce or it is even pre- anti-wear, lead to Often antiwear additive is added in the lubricating composition for being used for oilgear.When under stress, these additives are in gear table Protective layer is formed on face.Gear Contact surface is separated from each other and therefore reduces the abrasion on these surfaces by this protective layer.But It is, and not all antiwear additive can provide effective surface protection.

The present invention provides New Kind of Anti-Abrasion additive and/or friction modifiers, can be used for industrial gear, wind turbine In the lubricant compositions of machine, hydraulic device and automobile gear, with provide abrasion on reduced gear surface and/or friction and The gear microdot of reduction is lost.

Summary of the invention

In an aspect, the present invention relates to a kind of formula (I) compounds:

Wherein each R¹And R¹⁰It is same or different, and independently selected from C₁-C₂₀Straight chained alkyl, C₂-C₂₀Straight chain Alkenyl, C₃-C₂₀Branched alkyl and C₃-C₂₀Branched-chain alkenyl；

N is 1 to 7 integer；

R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹Each of be same or different, and be each independently selected from H, C₁- C₁₀Straight chained alkyl, C₂-C₁₀Straight-chain alkenyl, C₃-C₁₀Branched alkyl and C₃-C₁₀Branched-chain alkenyl；

X is selected from by H, hydroxyl and N (R¹¹)(R¹²) composition group；And

R¹¹And R¹²It is same or different, and is each independently selected from and is made of H, hydroxyl, alkyl, alkenyl and alkynyl Group.

In second aspect, the present invention provides a kind of lubricating additive concentrate, and it includes at least one formula (I) chemical combination Object.

In a third aspect, the present invention provides a kind of lubricating additive concentrate, and it includes at least one formula (I) compounds With one or more other additives.

In fourth aspect, the present invention provides a kind of lubricant compositions, and it includes a large amount of base oil and at least one Formula (I) compound.

In the 5th aspect, the present invention provides a kind of mobile metal surface of lubricant compositions lubrication machine component Method, the lubricant compositions include at least one formula (I) compound.

In the 6th aspect, the present invention provides the method for the abrasion on a kind of mobile metal surface of reduction machine part, The method includes with the lubricant compositions lubrication machine component comprising at least one formula (I) compound.

In another aspect, the present invention provides the method for the friction on a kind of mobile metal surface of reduction machine part, The method includes with the lubricant compositions lubrication machine component comprising at least one formula (I) compound.

In another embodiment, the present invention provides a kind of lubricant compositions comprising at least one formula (I) compound The method of lubrication machine component, wherein the machine part includes industrial gear, wind turbine gear, axle, differential mechanism, hair Motivation, crankshaft, speed changer, clutch, hydraulic device, slideway equipment and/or turbine.

Detailed description of the invention

Mean profile deviation caused by Fig. 1 shows being lost in for the erosion test of the microdot of one embodiment of the invention as microdot (ffm)。

Fig. 2 indicates that the microdot in the microdot erosion test for one embodiment of the invention loses region (GF) percentage.

Fig. 3 indicates the weight loss (W) in the microdot erosion test for one embodiment of the invention.

Specific embodiment

Invention disclosed herein is related to being suitable for the novel amino diphosphine of antiwear additive and/or friction modifiers additive component Phosphate compounds, the lubricating additive concentrate and lubricant compositions for respectively containing this kind of compound, and make and use Its method.

Although certain embodiments of the present invention can be described individually herein, those skilled in the art should be managed Solution, any one embodiment can be combined with any other one or more embodiments, and these combinations are in the scope of the present invention It is interior.

The embodiment for being related to formula (I) compound is including but not limited to following:

(1) formula (I) compound:

Wherein R¹And R¹⁰Each of be same or different, and independently selected from C₁-C₂₀Straight chained alkyl, C₂-C₂₀ Straight-chain alkenyl, C₃-C₂₀Branched alkyl and C₃-C₂₀Branched-chain alkenyl；

N is 1 to 7 integer；

X is selected from by H, hydroxyl and N (R¹¹)(R¹²) composition group；And

(2) compound of (1), wherein R¹And R¹⁰Each of be same or different, and independently selected from C₂-C₂₀ Straight chained alkyl.

(3) compound of (1), wherein R¹And R¹⁰Each of be normal-butyl.

(4) compound of (1), wherein R¹And R¹⁰Each of be ethyl.

(5) compound of (1) or (2), wherein each R¹It is 2- ethylhexyl.

(6) compound of (1) or (2), wherein each R¹⁰It is 2- ethylhexyl.

(7) compound of (1), wherein R¹And R¹⁰Each of be 2- ethylhexyl.

(8) compound of (1), wherein R¹And R¹⁰Each of be oil base.

(9) (1) arrives the compound of any of (8), wherein R²、R³、R⁴And R⁵Each of be H.

(10) (1) arrives the compound of any of (9), wherein R⁶、R⁷、R⁸And R⁹Each of be H.

(11) compound of any of (1) to (10), wherein n is 1 to 4 integer.

(12) compound of (11), wherein n is 1 or 2.

(13) compound of (1), wherein (a) R¹And R¹⁰Each of be same or different, and independently selected from C₂-C₂₀Straight chained alkyl；(b) R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹Each of be H.

(14) compound of (13), wherein R¹And R¹⁰Each of be same or different, and independently selected from C₂- C₁₀Straight chained alkyl.

(15) compound of (13) or (14), wherein (c) n is 1 to 4 integer.

(16) compound of (15), wherein n is 1 or 2.

(17) compound of any of (1) to (16), wherein X is hydroxyl.

(18) compound of any of (1) to (16), wherein X is N (R¹¹)(R¹²)。

(19) compound of (18), wherein R¹¹And R¹²It is same or different and is C₁-C₄Alkyl.

(20) compound of (19), wherein R¹¹And R¹²It is methyl.

(21) compound of any of (1) to (16), wherein X is H.

(22) compound of (1), wherein formula (I) compound is selected from:

(23) compound of (1), wherein formula (I) compound is selected from:

In one embodiment, the present invention relates to a kind of lubricating additive concentrates, and it includes formula (I) compounds.

In one embodiment, by the total weight of lubricant compositions, formula (I) compound is with about 0.01wt% to about The amount of 3wt% is present in lubricating additive concentrate.

In another embodiment, lubricating additive concentrate further includes one kind or more selected from the group being made up of Kind additive component: antioxidant, antiwear additive in addition, corrosion inhibitor, detergent, extreme pressure agent, dispersing agent, viscosity index (VI) change Into agent and friction modifiers.

In one embodiment, lubricant compositions of the invention include major amount of base oil with lubricant viscosity or Lubricating grease prepared therefrom and formula (I) compound.

In one embodiment, formula (I) compound is present in lubricant compositions with a certain amount of, to provide to lubricant The phosphorus of 100ppm to 1200ppm.

In another embodiment, lubricant compositions are further included adds selected from the one or more of group being made up of Add agent component: antioxidant, antiwear additive in addition, corrosion inhibitor, detergent, extreme pressure agent, dispersing agent, viscosity index improver And friction modifiers.

In another embodiment, the method for the present invention of the abrasion on the metal surface for reducing machine part includes apparatus There is the lubricant lubrication machine component of a effective amount of formula (I) compound, wherein formula (I) compound is selected from the group being made up of:

In one embodiment, machine part is selected from one of the following or multiple: industrial gear, wind turbine tooth Wheel, axle, differential mechanism, engine, crankshaft, speed changer, clutch, hydraulic device, slideway equipment and turbine.

It is a kind of reduce machine part mobile metal surface between abrasion method include lubricant compositions lubrication Machine part, the lubricant compositions include the major amount of base oil with lubricant viscosity or lubricating grease prepared therefrom with A effective amount of formula (I) compound.

In a preferred aspect, the present invention provides formula (I) compound and is used to reduce the mill between mobile metal surface Damage and/or the purposes for reducing the friction between mobile metal surface.For example, the present invention provides formula (I) compound for subtracting The purposes of few microdot erosion.This preferred aspect of the invention may be constructed the base of each of present invention disclosed herein method Plinth.

In certain embodiments, lubricating additive concentrate or lubricant compositions include at least one formula (I) compound And further include one or more additive components.This kind of concentrate or composition may include it is one or more have it is identical or Component of different nature.For example, comprising one or more formulas (I) compound and one or more additive components (such as One, two, or more of antioxidant, dispersing agent, detergent etc.) concentrate and lubricant compositions in model of the invention In enclosing.

As used herein, the moieties of term " alkyl " and the other groups being mentioned above are linear chain or branched chains Saturated hydrocarbons.Unless specified otherwise herein, otherwise alkyl preferably contains 1 to 30 carbon atom, for example, 1 to 20 carbon atom or 1 to 10 carbon atom.The representative example of alkyl includes but is not limited to methyl, ethyl, propyl, butyl, amyl, new penta Base, 2- ethylhexyl and similar group.

As used herein, term " alkenyl " refers to the linear chain or branched chain hydrocarbon chain containing at least one carbon-to-carbon double bond.It removes Non- to dictate otherwise, otherwise alkenyl preferably contains 2 to 30 carbon atoms, such as 2 to 20 carbon atoms or 2 to 10 Carbon atom.For example, term " C₂-C₄Alkenyl " refers to the alkenyl containing 2 to 4 carbon atoms.The representative example packet of alkenyl Include (but being not limited to) vinyl, 2- acrylic, 2- methyl -2- acrylic, 3- cyclobutenyl, 4- pentenyl, 5- hexenyl, 2- heptene Base, 2- methyl-1-heptenyl, oleyl (oleyl), 3- decene base, oleyl (olelyl) and similar group.

As used herein, term " alkynyl " refers to the linear chain or branched chain hydrocarbon chain containing at least one carbon-carbon triple bond.It removes Non- to dictate otherwise, otherwise alkynyl preferably contains 2 to 30 or 3 to 30 carbon atoms, such as 2 to 20 or 3 to 20 A carbon atom or 2 to 10 or 3 to 10 carbon atoms.For example, term " C₂-C₄Alkynyl " refers to containing 2 to 4 The alkynyl of carbon atom.The representative example of alkynyl include but is not limited to acetenyl, 2-propynyl, 3- butynyl, 4- pentynyl, 5- hexin base, 2- heptynyl, 3- decynyl and similar group.

As used herein, term " about " refers to approximate or close relative to an amount, and including exact amount.Citing For, phrase " about 1.0% " refers to about or close to 1.0%, but also includes lucky 1.0%.

As used herein, phrase " effective quantity ", which refers to, reaches required effect (such as reducing abrasion and/or friction) The amount of compound.

It is expected that formula (I) compound can be used as the additive in lubricating base oil.As used herein, term " base oil " or " basic material " refers to according to American Petroleum Institute (American Petroleum Institute；API) classification group I-V group The oil and animal oil of oil classification, vegetable oil (such as castor oil and lard), petroleum, mineral oil, synthetic oil and from coal or The oil of shale.American Petroleum Institute is as follows by these different basic material classification of type: Group I, is greater than 0.03wt% sulphur, And/or it is less than 90vol% saturate, viscosity index (VI) is greater than or equal to 80 and less than 120；Group II is less than or equal to 0.03wt% sulphur, and it is greater than or equal to 90vol% saturate, viscosity index (VI) is greater than or equal to 80 and 120；Group III, be less than or Equal to 0.03wt% sulphur, and it is greater than or equal to 90vol% saturate, viscosity index (VI) is greater than or equal to 120；Group IV, Suo Youju Alpha-olefin；Group V, it is all of Group I, Group II, Group III or Group IV basic material that basic material, which covers unclassified, Other basic materials.Group V basic material includes but is not limited to naphthenic oil and ester.The basic material of hydrotreating and catalysis are de- The basic material of wax generally falls into Group II and Group III classification due to its low-sulfur and arene content.Poly alpha olefin (Group IV base Plinth raw material) it is the synthetic base oil prepared by various alhpa olefins and substantially free of sulphur and aromatic hydrocarbons.

Group I, Group II and Group III are that mineral oil processes raw material.Group iv base oils contain real synthetic molecules Substance is prepared by the polymerization of ethylenically unsaturated hydrocarbons.Many Group V base oils are also real synthetic product, and can be wrapped Include diester, polyol ester, polyalkylene glycol, alkylated aromatic hydrocarbons, polyphosphate, polyvinylether and/or polyphenyl ether and similar Object, but can also be naturally occurring oils, such as vegetable oil.Although should be noted that Group III base oil derives from mineral oil, The stringent processing experienced of these fluids is so that its physical property is very similar to some real synthetics, such as PAO.Cause This can will be known as complex fluids from the oil of Group III base oil sometimes in the industry.

Formula (I) compound can be added to basis in the form of or mixtures thereof mineral oil or synthetic oil, animal oil, vegetable oil In oil.In general, mineral oil (alkane and cycloalkane) and its mixture can be used as lubricating oil or as lubricating grease medium.It also considers Lubricating grease, the aforementioned oil of any of them are used as alkali.

In addition to other additive components, formula (I) compound can be added in lubricating oil to form finished fluid.At certain In a little embodiments, the viscosity of finished fluid is ISO 10VG to ISO 680VG.In one embodiment, finished fluid includes profit Lubricating oil and formula (I) compound and viscosity are ISO 68VG to ISO 680VG.In another embodiment, finished fluid includes lubrication The compound of oil and formula (I) and viscosity are ISO 22VG to ISO 68VG.In another embodiment, lubricating composition includes lubrication Oil and formula (I) compound and SAE gear viscosity number are at least about SAE 70W or at least about SAE 75W.Lubricating composition can also be with With multiple levels, such as SAE 75W-80,75W-90,75W-140,80W-90,80W-40,85W-90,80W-90 or 80W- 140.Multigrade lubricant may include viscosity improver, be deployed together with the oil with lubricant viscosity to provide above-mentioned lubrication etc. Grade.

When lubricant is used as lubricating grease, lubricant is usually to be enough considering the desired amount of thickener and lubricating grease allotment The amount that total grease composition is balanced after the other additive components for including in object uses.Extensive multiple material can be used as thickener or Gelling agent.These may include conventional any one of metal salt or soap, such as calcium or lithium stearate or hydroxy stearic acid ester, It is scattered in lubrication medium with forming the amount of lubricating grease, consistency needed for presenting in an amount at least sufficient to imparting gained lubricant composition.It can use Other thickeners in lubricating grease composite include non-soap thickeners, such as clay and silica, aryl that surface is modified Urea, calcium complexes and similar material.In general, can be used will not melt or molten when using at desired temperatures in specific environment The grease thickener of solution；However, in all other aspect, commonly used in the hydrocarbon stream for being used to form lubricating grease that thickens or be gelled Any material of body can be used in the lubricating grease comprising formula (I) compound.

When synthetic oil or synthetic oil as lubricating grease medium are better than mineral oil or the mixture of mineral oil and synthetic oil When, various synthetic oils can be used.Typical synthetic oil includes that polyisobutene, polybutene, poly decene, siloxanes and silicone are (poly- Siloxanes).

The present invention provides lubricant compositions, and it includes the major amount of oily or prepared therefrom lubrications with lubricant viscosity Rouge and a small amount of formula (I) compound.It can be using formula (I) compound as single compound or as lubricating additive concentrate Component is added in the major amount of oily or prepared therefrom lubricating grease with lubricant viscosity.As used herein, primary amount Oil or lubricating grease refer to the amount of oil or lubricating grease in the composition in composition be greater than formula (I) compound amount.In general, Oil/grease amount is at least 50 weight %, for example, at least 70% or at least 90% of total composition.Similarly, if formula (I) is changed It closes the component that object is lubricating additive concentrate and lubricating additive concentrate is added in oil or lubricating grease, then a large amount of oil Or lubricating grease means that the amount of oil or lubricating grease in lubricant compositions is more than lubricating additive concentration in lubricant compositions The amount of object.Amount of formula (I) compound in lubricant compositions can for total composition about 0.001 weight % to 10 weight %, 0.005 weight % to 5 weight %, 0.01 weight % are between 2.0 weight %, 0.5 weight % to 2.0 weight % and 0.015 weight Measure % to 0.6 weight %.In some embodiments, lubricating composition can be containing about 0.005 weight % to 0.6 weight %, about 0.06 weight % to about 0.6 weight %, or about 0.02 weight % to about 0.5 weight %, or about 0.005 weight % to about 0.2 weight Measure formula (I) compound of %.

As mentioned above, formula (I) compound can easily be deployed into the profit suitable for various machine parts and component Lubricant composition.Lubricant compositions comprising formula (I) compound optionally further include one or more other additions Agent component or flux oil.The additive component list of following discloses is not detailed, and not specifically disclosed additive group herein It is well-known to one skilled in the art for dividing, and also may include in lubricant compositions.Without limitation, it can be used for this Additive component in the lubricant compositions of invention include antioxidant, antiwear additive in addition, corrosion inhibitor, detergent, Dispersing agent, extreme pressure agent, viscosity index improver, pour-point depressant, defoaming agent and anti-friction agent.

In one embodiment, the present invention provides a kind of lubricating additive concentrate, it includes formula (I) compound and at least A kind of other additive component and/or flux oil.One or more other additive components can be selected from: antioxidant, another Outer antiwear additive, corrosion inhibitor, detergent, dispersing agent, extreme pressure agent, viscosity index improver, pour-point depressant, demulsifier, defoaming Agent and friction modifiers.Flux oil can be any suitable oil or lubricating grease prepared therefrom with lubricant viscosity.

Formula (I) compound can be directly incorporated in the oil with lubricant viscosity.Alternatively, formula (I) compound can be with one Kind or the combination preparation of a variety of flux oils and/or other lubricating additives, to form lubricating additive concentrate.In general, lubrication adds Add agent concentrate by the specified weight hundred further with lubricating additive concentrate relative to final lubricant compositions total weight Divide and is incorporated in the oil with lubricant viscosity than (wt%).Selected wt% is commonly referred to as handling rate, and contains lubricating additive The lubricant compositions of concentrate are commonly referred to as finished fluid.

Antioxidant

Anti-oxidant compounds be it is known and including such as phenolate, phenol sulfide, olefine sulfide, sulphur phosphatization terpene, Sulfurised ester, aromatic amine, alkylated diphenylamine are (for example, nonyl diphenylamine, dinonyldiphenylamine, octyl diphenylamine, dioctyl two Aniline), phenyl-α-naphthylamine, be alkylated phenyl-α-naphthylamine, the non-aromatic amine that is obstructed, phenol, hindered phenol, soluble molybdenum compounds, Or mixtures thereof macromolecular antioxidant,.Single antioxidant or the combination of two or more can be used.

Hindered phenol antioxidant can contain sec-butyl and/or tert-butyl and be obstructed group as space.Phenolic group can be further Replaced by alkyl and/or the bridge joint group for being connected to the second aromatic group.The example for being suitble to hindered phenol antioxidant includes: 2, 6- di-t-butyl phenol, 4- methyl -2,6- di-t-butyl phenol, 4- ethyl -2,6- di-t-butyl phenol, 4- propyl -2,6- Di-t-butyl phenol or 4- butyl -2,6- di-t-butyl phenol or 4- dodecyl -2,6- di-t-butyl phenol.It is real one It applies in example, hindered phenol antioxidant can be ester and may include for example from 2,6- di-t-butyl phenol and alkyl acrylate The addition product of ester, wherein alkyl can contain about 1 to about 18, or about 2 to about 12, or about 2 to about 8, or About 2 to about 6, or about 4 carbon atoms.

Useful antioxidant may include diaryl amine and high molecular weight phenol.In one embodiment, lubricant oil composite can With the mixture containing diaryl amine Yu high molecular weight phenol, various antioxidants are enough to provide by lubricating oil composition The amount of the final weight meter of object at most about 5 weight % antioxidants exists.In some embodiments, amine lubricant oil composite is most Whole poidometer, antioxidant can be about 0.3 weight % to about 1.5 weight % diaryl amines and about 0.4 weight % to about 2.5 weights Measure the mixture of % high molecular weight phenol.

Can vulcanize with the example for forming the suitable alkene of olefine sulfide includes: propylene, butylene, isobutene, polyisobutene, penta Alkene, hexene, heptene, octene, nonene, decene, hendecene, laurylene, tridecylene, tetradecene, ten pentaenes, hexadecylene, 17 alkene, Or mixtures thereof octadecylene, 19 alkene, icosa alkene.In one embodiment, hexadecylene, 17 alkene, octadecylene, 19 alkene, 20 Or mixtures thereof alkene and its dimer, trimer and four polymer are especially suitable alkene.Alternatively, alkene can be Diels-Alder adduct (Diels- of diene (such as 1,3-butadiene) and beta-unsaturated esters (such as butyl propyleneglycol acid esters) Alder adduct)。

Another kind of olefine sulfide includes sulfide aliphatic acid and its ester.Fatty acid be usually obtained from vegetable oil or animal oil and usually Contain about 4 to about 22 carbon atoms.The example of suitable fat acid and its ester includes triglycerides, oleic acid, linoleic acid, palm oil Or mixtures thereof acid.In general, fatty acid is obtained from lard, pine tar, peanut oil, soybean oil, cottonseed oil, sunflower oil or its mixing Object.Fatty acid and/or ester can be mixed with alkene (such as alpha-olefin).

In lubricating composition, one or more antioxidants can about 0wt.% to about 20wt.% or about 0.1wt.% Range to about 10wt.% or about 0.5wt.% to about 5wt.% exists.

Other antiwear additive

In addition suitable antiwear additive example includes but is not limited to metal thiophosphate；Metal dialkyl phosphordithiic acid Salt；Phosphate or its salt；Phosphate；Phosphite ester；Phosphorus-containing carboxylic acid ester, ether or amide；Olefine sulfide；Containing thiocarbamate Compound, including thiocarbamate, alkylidene be coupled thiocarbamate and bis- (two thiocarbamoyls of S- alkyl Base) disulphide；And its mixture.Phosphorous antiwear additive is more fully described in European Patent No. 0,612 839.Two Metal in alkyl-dithio phosphate can be alkali metal, alkaline-earth metal, aluminium, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc.It is suitable Antiwear additive can be zinc dialkyl dithiophosphate.

Other antiwear additive can be with the about 0wt.% to about 15wt.% of lubricating composition total weight or about 0.05wt.% is arrived The range of about 10wt.% or about 0.01wt.% to about 5wt.% or about 0.1wt.% to about 3wt.% exists.

Detergent

Lubricant compositions are optionally including one or more neutral, low alkalinities or over-based detergent and its mixing Object.Suitable cleaners matrix includes: phenolate, sulfur-bearing phenolate, sulfonate, cup aromatic acid salt (calixarate), Liu Fang hydrochlorate (salixarate), salicylate, carboxylic acid, phosphoric acid, single thiophosphate and/or phosphordithiic acid, alkyl phenol, sulphur are coupled alkyl phenol Compound and methylene-bridged phenol.Suitable cleaners and preparation method are described in greater detail in many patent disclosures, including U.S. Patent No. 7,732,390 and references cited therein.

Detergent matrix can be used such as (but not limited to) alkali or alkaline earth metal below carrys out salinization: calcium, magnesium, potassium, Or mixtures thereof sodium, lithium, barium.In some embodiments, detergent not baric.Suitable detergent may include mahogany acid and The alkali or alkaline earth metal salt of long-chain list or di alkylaryl sulfonic acid, wherein the aryl is benzyl, tolyl and diformazan One of phenyl.

Over-based detergent additive is well-known in the art and can be alkali or alkaline earth metal height Alkaline clean agent addition agent.This kind of detergent additive can be by oxidizing metal object or metal hydroxides and matrix and two Carbon oxide gas reacts to prepare.Matrix is usually acid, such as following acid: the sulfonic acid that is for example replaced by aliphatic, by aliphatic Substituted carboxylic acid or the phenol replaced by aliphatic.

Term " high alkalinity " is related to metal salt, such as the metal salt with sulfonate radical, formate and phenol, present in Amount of metal is more than stoichiometry.These salt can have the level of conversion more than 100% (that is, it may include being greater than to convert acid to 100% of theoretical metal amount needed for its " standard ", " neutrality " salt).The statement " metal ratio " of MR is usually abbreviated as specifying According to known chemical reactivity and stechiometry, the change of total chemical equivalent of metal and metal in neutral salt in high alkalinity salt Learn the ratio of equivalent.In standard or neutral salt, metal ratio is one, and in high alkalinity salt, and MR is greater than one.This kind of salt is usually claimed It for high alkalinity, hyperalkaline or superbased salt, and can be the salt of organic sulfuric acid, carboxylic acid or phenol.

Over-based detergent can have 1.1: 1 or 2: 1 or 4: 1 or 5: 1 or 7: 1 or 10: 1 metal ratio.

In some embodiments, detergent can be used for reducing or preventing getting rusty in gear, axle or engine.

With the total weight of lubricant compositions, detergent can about 0wt.% arrived to about 10wt.% or to 0.1wt.% About 8wt.% or about 1wt.% exist to about 4wt.%.

Dispersing agent

Lubricant compositions can optionally further include or mixtures thereof one or more dispersing agents.Dispersing agent is usual Referred to as ashless type dispersants, because without containing the metal for forming ash content, and working as and being added to before being mixed into lubricant oil composite When in lubricant, it is generally not provided any ash content.Ashless type dispersants, which are characterized by, is attached to relatively high molecular weight hydrocarbon The polar group of chain.Typical ashless dispersant includes the long-chain alkenyl succimide that N- replaces.The long alkenyl that N- replaces The example of succimide includes polyisobutene succinimide, and the number average molecular weight of polyisobutene substituent group is about 350 to about 5000 or about 500 to about 3000.Succinimide dispersant and its preparation are disclosed in such as U.S. Patent No. 7,897, In No. 696 and U.S. Patent No. 4,234,435.Succinimide dispersant is usually by polyamine, usually poly- (ethylidene Amine) formed acid imide.

In some embodiments, lubricant compositions include at least one polyisobutene succinimide dispersing agent, are come Derived from polyisobutene of the number average molecular weight in about 350 to about 5000, or about 500 to about 3000 ranges.Polyisobutene fourth Imidodicarbonic diamide can use individually or with other dispersant packages.

In some embodiments, polyisobutene (PIB) (including when) can have greater than 50mol%, be greater than 60mol%, Greater than 70mol%, the terminal double bond content greater than 80mol% or greater than 90mol%.This kind of PIB is also referred to as high response PIB ("HR-PIB").HR-PIB of the number average molecular weight in about 800 to about 5000 ranges is suitable for embodiment of the disclosure.Often The non-high response PIB of rule is typically below 50mol%, is less than 40mol%, is less than 30mol%, is less than 20mol% or small In the terminal double bond content of 10mol%.

HR-PIB of the number average molecular weight in about 900 to about 3000 ranges can be suitable.This kind of HR-PIB is can It is commercially available or can be synthesized by polymerizeing isobutene non-chlorinated catalyst (such as boron trifluoride) in the presence of, as the U.S. is special Described in benefit No. 4,152,499 and U.S. Patent No. 5,739,355.When being used for aforementioned hot alkene reaction, due to enhancing Reactivity, HR-PIB can be improved reaction conversion ratio and reduce deposit formation.

A kind of suitable dispersing agent can be Mannich base (Mannich bases).Mannich base is by making higher molecular The material that alkyl-substituted phenol, polyalkylene polyamine and aldehyde (such as formaldehyde) condensation of amount are formed.Mannich base is more detailed Ground is described in U.S. Patent No. 3,634,515.

A kind of suitable dispersing agent can be high-molecular weight ester or half esteramides.

Dispersing agent can also be post-processed and reacting with any one of various reagents by conventional method.These reagents In have boron, urea, thiocarbamide, dimercaptothiodiazole, carbon disulfide, aldehyde, ketone, carboxylic acid, hydrocarbon replace succinic anhydride, maleic anhydride, nitrile, Epoxides, carbonic ester, cyclic carbonate, hindered phenolic ester and phosphorus compound.U.S. Patent No. 7,645,726, U.S.7, 214,649 and U.S.8,048,831 describes some suitable post-processing approach and after-treatment products.

With the total weight of lubricant oil composite, it can be enough to provide and be up to about the amount of 20 weight % and come using dispersing agent (if present).With the total weight of lubricant oil composite, the amount for the dispersing agent that can be used can be about 0.1wt.% to about 15wt.% or about 0.1wt.% to about 10wt.% or about 3wt.% to about 10wt.% or about 1wt.% to about 6wt.% or About 7wt.% to about 12wt.%.In one embodiment, lubricant oil composite utilizes mixed dispersant system.

Extreme pressure agent

The lubricant oil composite of this paper can also optionally contain one or more extreme pressure agents.Dissolve in the extreme pressure in oil (Extreme Pressure；EP) agent includes sulfur-bearing and the EP of sulphur containing chlorine agent, chlorinated hydrocabon EP agent and phosphorus EP agent.The example of this kind of EP agent It include: chlorinated wax；Organic sulfur compound and polysulfide, such as dibenzyldisulfide, bis- (chlorophenylmethyl) disulphide, two fourths Base tetrasulfide, the methyl ester of oleic acid, sulphurized alkyl phenols, sulfurized dipentene, vulcanization terpene and vulcanization diels-Alder Adduct；Phosphosulfurized hydrocarbon, such as the reaction product of phosphoric sulfide and turpentine oil (turpentine) or methyl oleate；Phosphide, such as Phosphorous acid dialkyl and phosphorous acid trialkyl, such as dibutyl phosphite, two heptyl ester of phosphorous acid, phosphorous acid dicyclohexyl maleate, phosphorous Sour amyl phenyl ester；Phosphorous acid diamyl phenyl ester, 13 ester of phosphorous acid, phosphorous acid distearyl ester and the phosphorous acid replaced by polypropylene Phenyl ester；Metal thiophosphate carbamate, such as dioctyl zinc dithiocarbamate and heptylphenol diacid barium；Alkyl and dioxane The amine salt of base phosphoric acid, the amine salt of the reaction product including such as dialkyldithiocarbamacompositions and propylene oxide；And it is mixed Close object.

EP agent can be with the about 0wt.% to about 15wt.% of lubricating composition total weight or about 0.05wt.% to about The range of 10wt.% or about 0.01wt.% to about 5wt.% or about 0.1wt.% to about 3wt.% exists.

Other friction modifiers

Lubricant oil composite herein can also optionally contain one or more friction modifiers.Suitable friction changes Property agent may include containing metal and metal-free friction modifiers, and may include (but being not limited to): imidazoline, amide, Amine, succimide, alkoxylated amines, alkoxylate ether amines, amine oxide, amidoamines, nitrile, glycine betaine, quaternary ammonium, imines, Amine salt, aminoguanidine, alkanolamide, phosphonate ester, metal-containing compound, glyceride, sulfurized fatty compound and alkene, sunflower oil and Other naturally-produced vegetable oil or animal oil, dicarboxylic ester, the ester of polyalcohol or partial ester and one or more aliphatic or virtue Fragrant race's carboxylic acid and the like.

Suitable friction modifiers contain the alkyl selected from or mixtures thereof straight chain, branch or aromatic hydrocarbyl, and can To be saturated or unsaturated.Alkyl can be made of carbon and hydrogen or hetero atom (such as sulphur or oxygen).Alkyl can be between about 12 To about 25 carbon atoms.In one embodiment, friction modifiers can be long-chain fatty acid ester.In one embodiment, long-chain rouge Fat acid esters can be monoesters or diester or (three) glyceride.Friction modifiers can be higher fatty acid amide, long-chain fat ester, length Chain fatty epoxide derivate or long-chain imidazoline.

Other suitable frictional modifying agent may include organic, ashless (without metal), unazotized organic friction modifiers.This Class friction modifiers may include the ester by forming carboxylic acid and acid anhydrides and reaction of alkanol, and generally include covalently bonded to parent The terminal polar group (for example, carboxyl or hydroxyl) of oiliness hydrocarbon chain.The example of organic ashless unazotized friction modifiers is generally Know for glyceryl monooleate (GMO), monoesters, diester and three esters containing oleic acid.Other suitable frictional modifying agent are described in In U.S. Patent No. 6,723,685.

Amine friction modifiers may include amine or polyamine.This kind of compound can have linear saturation or undersaturated alkyl Or mixtures thereof, and about 12 to about 25 carbon atoms can be contained.Other examples of suitable friction modifiers include alkoxy Change amine and alkoxylate ether amines.This kind of compound can have or mixtures thereof saturations or undersaturated straight chain alkyl.It can contain There are about 12 to about 25 carbon atoms.Example includes ethoxylated amine and ethoxylation ether amines.

Amine and amide can use as it is or with boron compound (such as boron oxide, halogenation boron, metaboric acid ester, boric acid or Boric acid monoalkyl ester, dialkyl ester or trialkyl ester) formed addition product or reaction product form use.Other suitable frictionals change Property agent is described in U.S. Patent No. 6,300,291.

With the total weight of lubricating composition, friction modifiers can about 0wt.% to about 10wt.% or about The amount of 0.01wt.% to about 8wt.% or about 0.1wt.% to about 4wt.% exists.

Viscosity index improver

Lubricant oil composite herein also optionally contains one or more viscosity index improvers.Suitable viscosity Index improver may include polyolefin, olefin copolymer, ethylene/propene copolymer, polyisobutene, hydrogenated styrene-isoamyl Diene polymer, styrene/maleate copolymer, hydrogenated styrene/butadiene copolymer, hydrogenated isoprene polymer, Alpha-olefin maleic anhydride multipolymer, polymethacrylates, polyacrylate, alkyl styrenes, hydrogenated alkenyl aryl Or mixtures thereof conjugated diene copolymer,.Viscosity index improver may include star polymer, and suitable example is described in beauty State discloses in the 2012/0101017th No. A1.

In addition to viscosity index improver or viscosity index improver is replaced, lubricant oil composite herein can also appoint Selection of land contains one or more dispersing agents viscosity index improver.Suitable viscosity index improver may include functionalization polyene Hydrocarbon, such as used the functionalized ethylene-propylene copolymer of reaction product of acylating agent (such as maleic anhydride) and amine；With amine function The polymethacrylates of change, or the esterification maleic anhydride-styrene copolymers reacted with amine.

With the total weight of lubricating composition, the total amount of viscosity index improver and/or dispersant viscosity index improvers It can be about 0wt.% to about 20wt.%, about 0.1wt.% to about 15wt.%, about 0.1wt.% to about 12wt.% or about 0.5wt.% to about 10wt.%.

It can readily determine that the effective quantity of the various additives component for specific composite, but for the mesh of explanation , provide these representative a effective amount of general guides.It measures and is provided with the weight % of finished fluid below.

Component	Example ranges (wt%)	Example ranges (wt%)
			Formula (I) compound	0.01-2	0.06-0.6
Dispersing agent	0-20	0.05-0.5
			Extreme pressure agent	0-5	0.5-2.0
Antirust agent	0-1.0	0.05-1.0
			Corrosion inhibitor	0-5	0.05~1.0
Demulsifier	0-5	0.002-0.05
			Defoaming agent	0-0.5	0.001-0.1
Diluent	0-10	1.0-5.0
			Antioxidant	0-5	0.05-0.3
Lubricating base oil	Surplus	Surplus

It includes hydraulic for wherein formula (I) compound and the industrial lubrication comprising its lubricating additive concentrate can be used to apply Oil, industrial gear oil, wind turbine machine oil, slideway machine oil, recycle oil and vapor wheel machine oil, gas turbine machine oil, gear oil, pressure Contracting machine oil, mist oil and machine tool lubrication agent.

Formula (I) compound and it can be used in transmission fluid comprising its lubricating additive concentrate.These fluids include Automotive fluid, such as manual transmission fluid, automatic transmission fluids, stepless transmission fluid, electronic-controlled power steering fluid and power Brake fluid.Formula (I) compound also may be incorporated into lubricating grease, such as automobile, industry and aviation grease and automobile chassis profit Lubrication prescription.

Formula (I) compound and it can be used in automobile gear or axle oil comprising its lubricating additive concentrate.Typically These oil are the automobile screw inclined planes and worm gear axle oil run under the conditions of extreme pressure, load and temperature, in high speed, low torsion The hypoid oil run under the conditions of square and low speed, high torque.

Engine oil containing formula (I) compound is also contemplated by the present invention.These oil include passenger vehicle engine oil, Heavy duty diesel engine oil, marine engine oil, locomotive and high speed car diesel engine.

The present invention also provides a kind of methods on lubricated metal surface.With lubricant compositions lubricated metal surface of the invention Abrasion and/or friction when can reduce mobile between metal surface.In one embodiment, the metal surface lubricated can be with It is machine part.Machine part may include axle, differential mechanism, engine, manual transmission, automatic transmission, stepless transmission, Clutch, hydraulic device, industrial gear, wind turbine gearbox, slideway equipment and/or turbine.

The present invention also provides a kind of method of lubricating transmission system, industry or metal working devices, it includes with including formula (I) lubricant compositions lubricating transmission system, industry or the metal working devices of compound.

Example

Synthetic route described in scheme 1 can be used to prepare formula (I) compound.One or more dialkylphosphites (II and II ') is reacted with one or more carbonyls (III and III ') and primary amine (IV), is generated formula (I) compound and is gone Water removal.

R¹And R¹⁰It is same or different, and independently selected from C₁-C₂₀Straight chained alkyl, C₂-C₂₀Straight-chain alkenyl, C₃-C₂₀ Branched alkyl and C₃-C₂₀Branched-chain alkenyl；N is 1 to 7 integer；R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹Each of be identical Or it is different, and it is each independently selected from H, C₁-C₁₀Straight chained alkyl, C₂-C₁₀Straight-chain alkenyl, C₃-C₁₀Branched alkyl and C₃-C₁₀Branch Alkenyl；X is selected from by H, hydroxyl and N (R¹¹)(R¹²) composition group；And R¹¹And R¹²It is same or different, and respectively independent Ground is selected from the group being made of H, hydroxyl, alkyl, alkenyl and alkynyl.

Scheme 1

Compound 1.

1 (R of compound¹、R¹⁰=normal-butyl, R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹=H, X=OH, n=1) by phosphorous acid two N-butyl, formaldehyde (being in paraformaldehyde form) and monoethanolamine synthesis.Under a nitrogen, at 60 DEG C by paraformaldehyde (118g, It 3.93mol) is added slowly in the reactor containing monoethanolamine (120g, 1.97mol).After adding paraformaldehyde, in vacuum Reaction mixture is heated to 95 DEG C under (45mmHg), while distillation goes to remove water.Then make to mix after no longer observing distillate It closes object and is cooled to 60 DEG C.Addition di-n-butyl phosphite (762.86g, 3.93mol) simultaneously reacts it 10 hours at 65 DEG C, with Obtain compound 1.The knot of compound is confirmed by P-31, H and C-13NMR spectrum and LC-MS (m/z=474.27 (M+I)) Structure.All nmr chemical displacements (δ) are provided with ppm.¹H NMR δ 4.1 (8H), 3.6 (2H), 3.2 (4H), 3.0 (2H), 1.7 (8H), 1.4 (8H), 0.9 (12H).¹³C NMR δ 65.78,60.12,59.12,50.9,32.71,18.76,13.61.31P NMRδ25.50。

Compound 2.

2 (R of compound¹、R¹⁰=ethyl, R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹=H, X=OH, n=1) it can be with compound 1 Similar mode, but use diethyl phosphite (361.75g, 2.62mol), paraformaldehyde (78.61g, 2.62mol) He Danyi It is prepared by hydramine (80.13g, 1.31mol).

Compound 3.

3 (R of compound¹、R¹⁰=butyl, R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹=H, X=OH, n=2) it can be with compound 1 Similarly, but di-n-butyl phosphite (582.28g, 3.00mol), paraformaldehyde (90.05g, 3.00mol) and 3- amino are used It is prepared by propyl alcohol (112.67g, 1.50mol).

Compound 4.

4 (R of compound¹、R¹⁰=ethyl, R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹=H, X=OH, n=2) it can be with compound 1 Similarly, but diethyl phosphite (350g, 2.54mol), paraformaldehyde (76.4g, 2.54mol) and 3- aminopropanol are used It is prepared by (95.1g, 1.27mol).

Compound 5.

5 (R of compound¹、R¹⁰=2- ethylhexyl, R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹=H, X=OH, n=1) it can be with The similar mode of compound 1, but using phosphorous acid bis- (2- ethylhexyl) (500g, 1.63mol), paraformaldehyde (49.1g, 1.63mol) prepared with monoethanolamine (50g, 0.82mol).

Compound 6

6 (R of compound¹、R¹⁰=butyl, R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹, X=H, n=7) it and can be similar with compound 1 Mode, but use di-n-butyl phosphite (388.2g, 2.00mol), paraformaldehyde (60.03g, 2.00mol) and n-octyl It is prepared by amine (129.25g, 1.00mol).

Compound 7

7 (R of compound¹、R¹⁰=butyl, R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹=H, X=N (CH₃)₂, n=2) it and can be with change Close the similar mode of object 1, but using di-n-butyl phosphite (543.52g, 2.80mol), paraformaldehyde (84.04g, 2.80mol) prepared with 3- (dimethylamino)-propyl amine (143.05g, 1.40mol).

Compound 8

8 (R of compound¹、R¹⁰=oil base, R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹=H, X=OH, n=1) it can be with compound 1 Similar mode, but use di-n-butyl phosphite (800g, 1.37mol), paraformaldehyde (41.2,1.37mol) and monoethanol It is prepared by amine (41.9,0.69mol).

Functional study

High-frequency reciprocating tester (High Frequency Reciprocating Rig；HFRR)

Make to respectively contain any one of above compound 1 to 8 lubricant test fluid experience HFRR test (according to ASTM-D6079-11), it is modified to use 400g mass to divide with 1mm stroke with the frequency test compound three of 20Hz at 80 DEG C Clock.The polishing scratch generated on oscillation ball and being contacted with the fixed disk being immersed in the fluid operated under restriction and controlled condition It is evaluated and is measured as unit of micron.HFFR test equipment is by vibrator, heating bath, specimen holder, test ball and test panel Composition.Fluid is tested to form lubricant, each in compound 1 to 8 is added in Group I mineral oil.Lubricant is surveyed Examination fluid respectively has the viscosity of ISO 100VG and containing the delivering of respective compound 1 to 8 by preparing as described above 300ppm phosphorus.

2-mL lubricant test sample (containing one of Group I mineral oil and compound 1 to 8) is placed in HFRR's It tests in reservoir.Non-rotating steel ball will be held and load has the vibrator arm of 400-g mass to reduce, until it contacts leaching completely Test panel not in lubricant fluid.When fluid temperature (F.T.) is stablized, make ball with 1 millimeter of stroke with the frequency of 20Hz and disk friction Three minutes.It maintains test fluid temperature (F.T.) and maintains envionmental humidity between 30% and 85%.Use microscope number phase Machine captures the image of polishing scratch, and measures and records the long axis of polishing scratch and the size of short axle, and calculates average grinding defect diameter (mean wear scar diameter；MWSD).

* without detectable abrasion

In upper table 1, the HFRR test result of compound 1 to 8 shows and the identical lubricant without formula (I) compound Composition is compared, and all lubricant compositions containing formula (I) compound all show the friction of reduced abrasion and reduction.

MTM-SLIM

Miniature tractor-space layer imager (Mini Traction Machine-Space Layer Imaging Machine；MTM-SLIM the frictional property through friction contact surface) is measured.In MTM-SLIM configuration, by 19.05mm steel ball It is carried on the steel disk surface that diameter is 46mm.Ball and disk are attached to axis and submerge in the lubricant.Ball and disk are independently driven It moves to generate rolling and sliding contact.Optical interference mensuration is raw for measuring dduring test additive films on the contact surface Long formation.The abrasion in load, lubricant temperature and contact surface that sensor measurement is applied.Pass through force sensor measuring Frictional force between ball and disk.

Typical full formula industrial gear fluid containing compound 1 is in MTM-SLIM in typical 100 tooth of ISO VG It is tested in wheel flow of oil.Fluid components and corresponding handling rate are shown in the following table 2.Test condition includes 50% sliding With rolling than (sliding speed and rolling speed), so that ball is with speed more faster than disk rotation.Football fan is 125mm/s, and disk speed is 75mm/s.Test 100 DEG C at a temperature of carry out (1) hour, and measure coefficient of friction.Dduring test, keep condition It is constant.Periodically capture interferes image to calculate thickness of the friction film layer relative to the time dduring test.As shown in table 3, In first time test, apply the contact pressure of 2GPa, wherein load is 20N.In second of test, apply the contact of 3GPa Pressure, wherein load is 75N.

MTM-SLIM test as the result is shown in table 3.The result shown in the table can be extrapolated to other formulas (I) chemical combination Object.The result shows that the phosphorous molecule of formula (I) compound forms phosphorus film under high load.Similarly, containing formula (I) compound Fluid forms phosphorus film under high load.

The erosion of FVA microdot

Microdot erosion is the fatigue rupture of surfacing used in gear train.Need the additive in gear fluids to prevent Microdot erosion only occurs.The microdot erosion that test GF-C/8.3/90 is used to measure lubricant is lost according to the microdot of FVA- information table 54/7 Load capacity and consist of two parts；Load stage test, is then durability test.

According to FVA- information table 54/7, test in test GF-C/8.3/90 is lost in microdot and contains compound 1 and with ISO The typical full formula industrial gear fluid of VG 100.Fluid components and corresponding handling rate are shown in the following table 4.Modification is surveyed Examination, so that only implementing the load stage part of test.This is enough the microdot erosion load capacity for determining fluid.

Microdot erosion test as the result is shown in fig. 1, fig. 2 and fig. 3.Fig. 1 shows that the mean profile caused by microdot erosion is inclined Poor (ffm).As indicated, the load stage (16 hours/load stage) of test run time is shown in left side, and durability test is transported The row time (80 hours/load stage) is shown in right side.Test condition is as follows:

A. gear-type: C

B. tooth pitch linear velocity: 8.3m/s

C. lubricant inject temperature: 90 DEG C

Fig. 2 shows the percentage (%) of microdot erosion area GF.As indicated, (16 is small for the load stage of test run time When/load stage) it is shown in left side, and durability test runing time (80 hours/load stage) is shown in right side.Test condition with Condition is identical those of shown in figure 1 above.

Fig. 3 shows weight loss (W).As indicated, the load stage (16 hours/load stage) of test run time is shown in Left side, and durability test runing time (80 hours/load stage) is shown in right side.Shown in test condition and figure 1 above that A little conditions are identical.

As shown in Fig. 1 to Fig. 3, have lower mean profile inclined during load stage with the gear of test fluid lubrication Difference, without the erosion of detectable microdot and lower weight loss.The instruction of these results, it is identical as what it is without formula (I) compound Lubricant compositions are compared, and formula (I) compound (including compound 1), which provides, well arrives excellent microdot erosion protection.Contain formula (I) The fluid of compound (including compound 1) can be classified as " high microdot erosion load capacity " fluid.

The test of FAG FE8 bearing

Many gear trains contain roller bearings element.It needs to carry out proper lubrication to these bearings, it is negative in height to prevent Carry lower abrasion.Lubricant protects the ability of bearing element that can test (DIN 51819-3 by FAG FE8 bearing；2 operations； 80kN is run at 80 DEG C every time, continues 80 hours) it is tested.

It tests in the FAG FE8 bearing test of above-mentioned reference containing compound 1 and with the typical case of ISO VG 100 Full formula industrial gear fluid.Fluid components and corresponding handling rate are shown in the following table 4.At the end of test, observe flat The only roller bearings abrasion of 1mg.This test is 30mg or lower by grade.

More temperature high-frequency reciprocating tester (Multiple Temperature High Frequency Reciprocating Rig；HFRR)

Make comprising the complete of above compound 1, two grease of hydrogen phosphite (DOHP) or octadecylphosphonic acid dimethyl ester (DMOP) It is formulated hydrodynamic lubrication fluid experience multi-temperature HFRR test (according to ASTM-D6079-11), it is modified at 70 DEG C, 100 DEG C and 130 4N frictional force is used at DEG C, 400g mass and 1mm stroke are tested compound three minutes with the frequency of 20Hz at each temperature.It is logical The polishing scratch for contacting with the fixed disk being immersed in the fluid operated under restriction and controlled condition and generating on oscillation ball is crossed to be commented Estimate and is measured as unit of micron.HFFR test equipment is made of vibrator, heating bath, specimen holder, test ball and test panel. The component of test fluid is listed in Table 5 in the form of the weight % of finished fluid.

The test sample of 2-mL lubricant A to F is put into the test reservoir of HFRR.Non-rotating steel ball will be held and born The vibrator arm for being loaded with 400-g mass reduces, until its contact is totally submerged the test panel in lubricant fluid.When fluid temperature When degree is stablized, ball is set to rub three minutes with 1-mm stroke with the frequency of 20Hz and disk under each test temperature, wherein each Suspend friction during temperature change.Envionmental humidity is maintained between 30% and 85%.It is caught using microscope digital camera The image for obtaining polishing scratch measures and records the long axis of polishing scratch and the size of short axle, and calculates average grinding defect diameter (MWSD).Fluid A To F and control, the results are shown in Table 6.

* comparative fluid is identical as fluid A-F but without DOHP, DMOP or compound 1.

In multi-temperature HFRR test, the compound of the present invention provides MWSD more lower than conventional constituents.

Although detailed herein and describe the particular embodiment of the present invention, but the invention is not restricted to this.It provides It is discussed in detail above as demonstration example of the invention, and is not construed as constituting any limitation of the invention.Modification will To those skilled in the art it is clear that and not departing from all modifications of purport of the invention and being intended to cover in appended right In the range of claim.

Claims

1. a kind of formula (I) compound:

Wherein R¹And R¹⁰Each of be it is same or different, independently selected from C₁-C₂₀Straight chained alkyl, C₂-C₂₀Straight chain alkene Base, C₃-C₂₀Branched alkyl and C₃-C₂₀Branched-chain alkenyl；

N is 1 to 7 integer；

R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹Each of be same or different, and be each independently selected from H, C₁-C₁₀Directly Alkyl group, C₂-C₁₀Straight-chain alkenyl, C₃-C₁₀Branched alkyl and C₃-C₁₀Branched-chain alkenyl；

X is selected from by H, hydroxyl and N (R¹¹)(R¹²) composition group；And

R¹¹And R¹²It is same or different, and is each independently selected from the group being made of H, hydroxyl, alkyl, alkenyl and alkynyl.

2. compound according to claim 1, wherein R¹And R¹⁰Each of be C₁-C₁₀Straight chained alkyl.

3. compound according to claim 1 or 2, wherein R²、R³、R⁴And R⁵Each of be H.

4. according to claim 1 to compound described in any one of 3, wherein R⁶、R⁷、R⁸And R⁹Each of be H.

5. compound according to any one of claims 1 to 4, wherein n is 1 or 2.

6. wherein X is hydroxyl according to claim 1 to compound described in any one of 5.

7. wherein X is N (R according to claim 1 to compound described in any one of 5¹¹)(R¹²), and R¹¹And R¹²It is C₁-C₄Alkane Base.

8. wherein X is H according to claim 1 to compound described in any one of 5.

9. compound according to claim 1, wherein

(a)R¹And R¹⁰Each of be identical and for C₁-C₂₀Straight chained alkyl；

(b)R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸And R⁹Each of be H；And

(c) n is 1 or 2.

10. compound according to claim 1, wherein the formula (I) compound is selected from:

11. compound according to claim 1, wherein the formula (I) compound is selected from:

12. a kind of lubricating additive concentrate, it includes according to claim 1 to compound described in any one of 11.

13. lubricating additive concentrate according to claim 13, wherein the lubricating additive concentrate further wraps Containing selected from the one or more additive components of group being made up of: antioxidant, antiwear additive in addition, corrosion inhibitor, Detergent, extreme pressure agent, dispersing agent, viscosity index improver and friction modifiers.

14. a kind of lubricant compositions, it includes:

A) a large amount of base oil；With

B) according to claim 1 to compound described in any one of 11.

15. a kind of method of the mobile metal surface of lubrication machine component, it includes with lubrication according to claim 14 Agent composition lubricates the surface.